|Publication number||US3906033 A|
|Publication date||Sep 16, 1975|
|Filing date||Dec 18, 1972|
|Priority date||Dec 4, 1969|
|Publication number||US 3906033 A, US 3906033A, US-A-3906033, US3906033 A, US3906033A|
|Inventors||Hans Rudolf Biland, Max Duennenberger, Christian Luethi|
|Original Assignee||Ciba Geigy|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (1), Referenced by (24), Classifications (33)|
|External Links: USPTO, USPTO Assignment, Espacenet|
ite States Biland et al.
[4 1 Sept. 16, 1975 OXALIC ACID DIARYLAMIDES  Inventors: Hans Rudolf Biland, Basel; Max
Duennenberger, Frenkendorf; Christian Luethi, Muenchenstein, all of Switzerland Related U.S. Application Data  Continuation-in-part of Ser. No. 879,964, Dec. 4, 1969, abandoned, which is a division of Ser. Nov 599,363, Dec. 6, 1966, Pat. No. 3,542,573.
 U.S. Cl. 260/479 R; 260/476 R; 260/473 F; 260/459 NC; 260/465 D; 260/513 R;
260/518 R; 260/556 B; 260/558 A; 260/559  Int. Cl. C07C 103/30  Field of Search 260/559, 479, 473, 476
 References Cited FOREIGN PATENTS OR APPLICATIONS 1.332.227 6/1963 France 260/559 Primary E.\'uminerHarry l. Moatz  ABSTRACT Disclosed are oxalic acid diarylamides as ultraviolet absorbing agents for organic materials, the oxalic acid diarylamides being compounds of the formula ANHCO-CONH-A in which A represents a member selected from the group consisting of in which Z represents a member selected from the group consisting of a linear or branched alkyl group with 1 to 18 carbon atoms, an acetyl, butyryl, lauroyl, octadecanoyl, benzoyl, para-tertiary butylbenzoyl or para-chlorobenzoyl group, a benzyl group, a carbalkoxyalkyl group with a total of up to 12 carbon atoms, an allyl group and a mono-halogenalkyl group with up to 8 carbon atoms; Z represents an alkyl or monohalogenalkyl group containing 1 to 18 carbon atoms; R represents an alkyl group containing 1 to 12 carbon atoms, w is 1, 2 or 3; X represents a member selected from the group consisting of an alkyl group with up to 12 carbon atoms, a halogen atom, a phenyl and a cyclohexyl group; and Y and Y each stands for hydrogen, an alkyl or alkoxy group with 1 to 8 carbon atoms, or Y may also represent a phenyl group; W represents an alkyl group with l to 18 carbon atoms or a carbalkoxyalkyl group with 3 to 8 carbon atoms.
9 Claims, No Drawings This is a continuation-in-part of our copending application Ser. No. 879,964 filed Dec. 4th, 1969, now abandoned which in turn, is a divisional application of Ser. No. 599,363, filed Dec. 6, 1966, now U.'S. Pat. No. 3,542,573.
The present invention provides symmetrical oxalic acid diarylamides that have proved particularly suitable for the protection of organic materials, which may be damaged by the action of light, especially ultraviolet rays, in a variety of ways, from the action of such irradiation.
While it is already known that certain oxalic acid bis hydroxyarylamides are suitable as light filters against ultraviolet irradiation, it had been thought in the past that the light stability of such compounds is conditional upon the presence of a free hydroxyl group in orthoposition to the amide nitrogen. Contrary to this assumption it has now been found thata large group of oxalic acid diarylamicles that do not conform with the said prerequisite are not only ultraviolet absorbers producing excellent results in industrial applications but,
surprisingly, even display a higher light stability. The symmetrical oxalic acid diarylamides ofthe formula 4 5 R5 R (1) I are homogeneously distributed in the organic materials, to be protected, or applied to the surface of said materials, or the materials to be protected are placed underneath a filter layer incorporating the compounds defined, In the formula (1) the symbols R to R each represents a hydrogen atom, a halogen atom, a substituent containing up to 20 carbon atoms from the series alkyl, substituted alkyl, benzene radical, benzyl group, a nitrile group, a possibly substituted alkoxy group, alkenyloxy group, an aliphatic or aromatic acyl group, one of the groups OCOHNX, CONH-X or SO NHX (where X stands for hydrogen, alkyl or aryl), a group COOY or -SO Y (where Y stands for hydrogen, alkyl, aryl or a salt-formingcation), a nitro group, an amino group or an acylamino group. The substituents R and R or R and R together with the benzene ring to which they are attached may also form a fused on six-membered carbocycle, and where a. each benzene nucleus contains at most two substituents -OCONH-X, CONHX, SO- NH-X, COOY, -S -,X, alkoxy or alkenyloxy, b. each benzene nucleus contains at most three of the other substituents different from hydrogen, and c. at least one of the substituents R to R is different from hydrogen. I Within the scope of this definition halogen is, for example, above all chlorine or bromine; alkyl is a branched'or linear alkyl radical having a small number of carbon atoms (C to C,,) or higher alkyls containing 5 to 18 carbon atoms (for example octyl, 'dodecyl and the like), a substituted alkyl radical'being'chloralk yl, bromalkyl, hydroxyalkyl, alkcnyloxyalkylg:*carboxyalkyl or carbalkoxyalkyl; a substituted alkoxy group is a halogenalkoxy, cyanalkoxy, hydroxyalkoxy, carbalkoxyalkoxy, SO X or a phenylalkoxy group; alkenyloxy is above all allyloxy;,an acyl group is, for example, acetyl, butyryl, lauroyl, octadecanoyl, benzoyl, paratertiary butylbenzoyl or para-chlorobenzoyl; acylamino groups are acetylamino and benzoylamino; amino groups may also be substituted, being methylamino or ethylamino, as well as the anilino groups. Within the scope of the formula l there are also the symmetrical compounds of the formula in which R,, to R are identical or different and each represents a hydrogen atom, a halogen atom, an alkyl or alkoxy group containing 1 to 18 carbon atoms, or a phenyl group, and in which a. each benzene nucleus contains at most two alkoxy groups, b. each benzene nucleus contains at most three substituents different from hydrogen, and c. at least one of the substituents R to R is different from hydrogen. Within the scope of the formula (1) there are also compounds of the formula in which R,; to R are identical or different and each represents a hydrogen atom, an aliphatic or aromatic acyl group containing 1 to 12 carbon atoms, one of the groups OCOHNX, CONHX or SO- NHX (where X stands for hydrogen, an alkyl group with l to 4 carbon atoms or phenyl), a group COOY or -SO Y (where Y is hydrogen, alkyl with l to 4 carbon atoms, phenyl, or. an alkali metal, ammonium or amine salt ion) and where each benzene nucleus contains one or two of the above-mentioned sub stituents different from hydrogen and at least one of the substituents R',, to R,,, is different from hydrogen.
In the case of the aniline or substituted aniline derivatives compounds of the formula are of practical interest. In this formula R and R are identical or different and each represents chlorine, bromine,,alkyl with l to 4 carbon atoms, alkoxywith l to 18 carbon atoms or a nitro group, or one of the substituents R or R represents a hydrogen atom, a carboxylic acid group, a carboxylic acid alkyl ester group containing l to 8 carbon atoms in its alkyl grouping, a sulphonic acid group or a sulphonamide group, or R represents an etherified or acylated hydroxyl group which is etherified (especially alkyl ethers) or acylated with a suitable group containing 1 to 18 carbon atoms. Some variants of such types of compounds correspond to the following formulae in which R represents a hydrogen atom, or an alkoxy group with 1 to 18 carbon atoms, with the proviso that at least one R per phenyl group represents such an alkoxy group,
R represents a hydrogen atom, a chlorine or bromine atom, with the proviso that at least one R per phenyl group represents one of these halogen atoms, and
R represents a hydrogen atom or an alkyl group with l to 4 carbon atoms, with the proviso that at least one R per phenyl group represents such an alkyl group,
Another type of compound suitable for protecting a-olefine polymers and polyvinylchloride corresponds to the general formula R O NH GO CO 111i O-R where R is an alkyl group with up to 18 carbon atoms, a benzyl group, an acyl group or an ally] group. In this group there are also compounds of the formula o .4111 co 00 1mwhere R represents a methyl, ethyl, octyl or octadecyl radical, The present invention provides symmetrical oxalic acid diarylamides of the formula ANHCO-CONH-A in which A represents a member selected from the group consisting of CH w 2 in which Z represents a member selected from the group consisting of a linear or branched alkyl group with 1 to 18 carbon atoms, an acetyl, butyryl, lauroyl, octadecanoyl, benzoyl, para-tertiary butyl-benzoyl or para-chlorobenzoyl group, a benzyl group, a carbalkoxyalkyl group with a total of up to 12 carbon atoms, an allyl group and a mono-halogenalkyl group with up to 8 carbon atoms; Z represents an alkyl or monohalogenalkyl group containing 1 to 18 carbon atoms; R represents an alkyl group containing 1 to 12 carbon atoms, w is l, 2 or 3; X represents a member selected from the group consisting of an alkyl group with up to 12 carbon atoms, a halogen atom, a phenyl and a cyclohexyl group; and Y to Y each stands for hydrogen, an alkyl or alkoxy group with l to 8 carbon atoms, or Y may also represent a phenyl group; W represents an alkyl group with l to 18 carbon atoms. or a carbalkoxyalkyl group with l to 8 carbon atoms, preferably 3 to 8 carbon atoms.
Ofspecial value within the scope of the formula 10) are those compounds which correspond to the formula and more especially those oxalic acid diarlyamides In the above formulae (1 l) and (12) Z, X and Y to Y have the same meanings as in formula (10). In formula l 1 preferably only one or two of the symbols Y, to Y and X represent substituents different from hydrogen atoms, as indicated above.
A subgroup of compounds of the above formula l 1 which are particularly valuable for practical use in cludes also those compounds of the formula l l as defined, in which, however, at least one of the substituents Y or X or both these substituents represent a tertiary butyl group.
Specific groups of compounds according to the above general formulae correspond to the following formulae (where Z has the meaning defined above):
Of special importance are also oxalic acid diarylamides of the formula -1TH CO-CO-- NH" in which w l. 2 or 3 and R represents an alkyl radical with l to 12 carbon atoms; also oxalic acid diarylamides of the formula in which Z represents an alkyl group with l to 18 carbon atoms or a halogenalkyl group, preferably monohalogenalkyl.
From the group of the naphthylamine derivatives according to the general formula (1 there may be mentioned, for example, those of the formula In this formula the brackets indicate that both a-naphthylamine and ,B-naphthylamine derivatives are possible; R represents a hydrogen atom, a lower alkyl group with 1 to 4 carbon atoms, a sulphonic acid group or an etherified hydroxyl group; m l or 2 in the case of the sulphonic acid group, but otherwise it is I.
From among the novel naphthylamine derivatives there may be mentioned above all those which have already been described in connection with formula :hat is to say primarily compounds of the formula n which W represents an alkyl group with l to 18 car- )Ol'l atoms or an carbalkoxyalkyl group with l to 8 car on atoms, preferably 3 to 8 carbon atoms.
From the large variety of oxalic acid diarylamides hat can be used in this invention there may be menioned the following non-limiting examples: Oxalic acid iarylamides derived from the under-mentioned ani nes: Aniline, 2-chloraniline, 4chloraniline, 3- hloraniline, 2,4-dichloraniline, 3,4-dichloraniline,
,4,6-trichloraniline and the corresponding bromani-- naphthylamine and of the following sulphonic acids the naphthylamines: l-naphthylamine-4-sulphonic id, 1 l-naphthylamine-5 sulphonic acid, iaphthylamine-8-sulphonic acid. 2-naphthylamine-5- phonic acid, 2-naphthylamin'c-4,8-(lisulphonic acid,
8 2-naphthylamine6,8-disulphonic acid, 8hydroxyl naphthylamine 4-sulphonic acid, 8hydroXy-2 naphthylamine6-sulphonic acid, 8-hydroxyl naphthylamine-4,6-disulphonic acid, 8-hydroxyl.-
naphthylamine-3,6-disulphonic acid and 8-hydroxy-2- naphthylamine-3,o-disulphonic acid.
The oxalic acid bis-arylamides of the general formula (1) are accesible by known methods, for example, by reacting oxalic acid compounds of the general formula in which Q represents a halogen atom, such as chlorine,
or the hydroxyl group or the OT group, T representing an aliphatic or aromatic hydrocarbon radical, preferably the methyl or ethyl group, with arylamines of the benzene or naphthalene series corresponding to the formula (II) R HZN R3 1 in which R to R have the meanings given in formula (I) substantially in the molecular ratio of 1:2, at temperatures between 0 and 220C in solution or in a melt, in the presence of an inert solvent, such as benzene, dichlorobenzene, tetrachlorethane or diethylcarbitol, if desired or required in the presence of a catalyst, such as boric acid, the reaction being conducted in such manner that hydrohalic acid, water, or alcohols or phenols are split off, and liquid byproducts are eliminated from the reaction mixture, preferably by azeo tropic distillation.
Compounds in which the radicals R to R are ether or ester groups can also be obtained from intermediate products containing phenolic hydroxyl groups by subsequent etherification or esterification in per se conventional manner. The novel symmetrical oxalic acid diarylamides of the formula ANHCOCON- H.A (I0) i where A has the same meaning as previously described are also synthesized by the above described process by reacting primary amines or the formula;
HO a: H0 H0 H N 1 H 1 2 2 a N 2 2 O x I it where Y Y Y X. has the same meaning as previously defined with oxalic acid compounds of formula (I). Then the groups Z, W, 2,, R where Z, W, Z, R have the same meaning as in formula (10), are introduced by esterification or etherification of the free phenolic group of the resulting product. Alternatively the groups Z, W, Z R can be initially introduced by etherification of the phenolic group of the primary amines of formula 10 a, 10 b, 10 c, 10 d, and then subsequent condensation of the resulting ether with oxalic acid compound of formula (I) to give the final product. The procedure of esterfication or etherifi- OH H C cation of phenolic group which leads to esters, ethers,
alkylethers, alkenylethers is fully described in Fr 2 A few examples of the reagents which can be used to esterify or etherify the phenolic group of the above described compounds are, benzoyl chloride, p-
NH m 2 H -H -H c 2 1 H000 H20 I 000 2 2 El HC2OOC [1 0 H O 2 OH CLI OH 2 NH 2 2 61 OH chlorobenzoyl chloride, chloroethyl acetate, 3- chloroethyl propionate, 4-chloroethyl butyrate, etc. These reagents as well as others are available from Aldrich chemical company, Fluka A.G. Chemise Fabrik and other well known chemical companies,
Some of the starting materials are commercially available while others could be obtained from available compounds by known methods. The conventional methods consist of introducing nitrogen functions such as NO NO, -N=NAr, in ortho-position to the phenolic group of available phenol or naphthol and then subsequent reduction of the nitrogen function to amino group. A good yield of the desired aminophenol or aminonaphthol is usually obtained, since the nitrogen function is introduced exclusively in the orthoposition to the phenolic group when the para-position is blocked by substituents as in formulae 10 a, and 10 b. Illustrative examples of these conventional methods are given below.
a. Viu-Nitration and subsequent reduction 2 H (at U on OH The method of preparation of the above phenols is fully described in J. Am. chem. Soc., 71,1265 (1949), 76,4985-4988 (1954).
b. Viu Nitroso-derivative and subsequent reduction 10 The method of preparation of this naphthol is described in Org. Syntheses, Coll. Vol., II 33 (1943) c. Via Azo-derivative and subsequent reduction The method of preparation of the above compounds is 0 fully described in Ann., 369,209 (1909), Ber., 39,2494
(1906 J. Amer. chem. Soc., 71,1265 (1969), 76,4985 1954).
By employing the above methods the starting materials listed below are synthesized.
Some of the aminophenolic ethers employed as starting 35 materials are commercially available as for example 2- methoxyaniline, 2-ethoxyaniline, while others are syntherized by known methods. The most common method consist of etherification of the available phenol, nitration of the resulting phenolicether and subsequent reduction of the nitro group to amino group. I1-
lustrative examples are the following:
NH NH H Co 2 cuii 2 Ngca H.5CO oca H 2 11 Cl 00 11 3:11 N
2 H5C (I: CH.
5 OC H n NH NH H o- H an 5 OH OH H c g 2 Isooc'tyl 2 5 ca OH OH Isooctyl W Q Isooc cyl- OH H OH tert. amyl 2 tert.amyl
The preparation of the above compounds is more fully described in J. Amer. Chem. Soc., 76,4985 (1954), U.S. Pat. No. 2,581,972 and British intelligence official subcommitte, Final Report, 986, I 1946) The preparation of aminophenol corresponding to formula d) is described in detail in J. Chem. Soc, 980, (1954).
The compounds of the above formulae (1) and the following are in principle suitable for stabilizing and protecting all those organic materials which are in any form damaged or destroyed upon exposure to ultraviolet rays. Such dosage due to the effect of the same agent, namely ultraviolet irradiation, may have widely disparate results, for example discoloration, changes in the mechanical properties (brittleness, fissuring, tear strength, flexural strength, abrasion resistance, elasticity, aging), triggering of undesired chemical reactions (decomposition of delicate chemical substances, for example medicaments), photochemically induced rearrangements, oxidation and the like (for example of oils containing unsaturated fatty acids) the causing of burns and irritation (for example on human skin) and the like.
Accordingly, the organic materials to be protected may belong to a wide variety of types of substances and be present in widely different processing stages and physical states, whereas they all have the common characteristic of being sensitive towards ultraviolet irradiation.
Organic materials of this kind may be of a high molecular or low molecular nature.
As nonlimiting examples of low molecular and high molecular substances that can be protected or stabilized by compounds of the instant invention, there may be mentioned:
Organic natural substances used for pharmaceutical purposes (medicaments), ultraviolet-sensitive dyestuffs, compounds which in the form of victuals or when present in victuals are decomposed by irradiation (unsaturated fatty acids in oils) and the like.
As examples or organic substances of high molecular weight there may be mentioned:
I. Synthetic organic materials of high or higher molecular weight such as:
a. Polymerization products based on organic compounds containing at least one polymerizable carbon-to-carbon double bond, that is to say their homopolymers or copolymers as well as their aftertreating products, for example crosslinking, grafting or decomposition products; diluted polymers; modification products obtained by modifying reactive groupings in the polymer molecule and the like, for example polymers based on 01,,B-unsaturated carboxylic acids (for example acrylates, acrylamides, acrylonitrile), of olefinic hydrocarbons, for example a-olefines, ethylene, propylene or dienes, that is to say also rubbers and rubberlike pol ymers (also socalled ABS polymers), polymers based on vinyl and vinylidene compounds (for example styrene, vinyl esters, vinylchloride, vinyl alcohol), of halogenated hydrocarbons, of unsaturated aldehydes and ketones, allyl compounds and the like;
b. other polymerization products obtainable, for example, by ring opening, for instance polyamides of based on bifunctional or polyfunctional compounds containing condensable groups, their homocondensates and cocondensate as well as their after-treatment products, such, for esample, as polyesters [saturated (e.g. polyehtylene terephthalate) or unsaturated (e.g. maleic aciddialcohol polycondensates and their crosslinked products with copolymerizable vinyl monomers), linear or branched (also those based on polyhydric alcohols, e.g. alkyd resins)], polyamides (e.g. hexamethylenediamine adipate, maleinate resins, melamine resins, phenolic resins (e.g. novolaks), aniline resins, furan resins, carbamide resins and their precondensates and similarly constituted products; polycarbonates, silicone resins and the like.
d. Polyadducts, such as polyurethanes (crosslinked and not crosslinked); epoxy resins.
ll. Semisynthetic organic materials, for example cellulose esters and mixed esters (cellulose acetate or propionate), nitrocellulose, cellulose ethers, regenerated cellulose (viscose rayon, cuprammonium cellulose) or their after-treatment products; casein synthetics.
III. Natural organic materials of animal or vegetable origin, for example those based on cellulose or proteins such as wool, cotton, silk, bast, jute, hemp, pelts and hairs, leathers, finely divided wood pulp, natural resins (such as colophony, especially lacquer resins), gelatin,
' glues, also rubber, gutta percha, balata and their aftertreatment and modification products, degradation products, products accessible by modification of reactive groups.
The organic materials concerned may be at widely differing stages of their processing (raw materials, semifinished products or finished products) and physical states. They may be in the form of products shaped in a wide variety of ways, that is to say, for example, as predominantly three-dimensional objects such as sections, vessels or components of a great variety, chips or granules, foamed products; predominantly twodimensional materials such as films, foils, lacquers, impregnations or coatings or predominantly unidimensional materials such as filaments, fibres, flocks, bristles or wires. The said materials may also be in unshaped states in a wide variety of homogeneous or inhomogeneous forms of distribution and physical states, for example in the form of powders, solutions, normal and reversed emulsions (creams), dispersions, latices, sols, gels, putties, waxes, adhesives or pore fillers, and the like.
Fibrous materials may be used in a wide variety of processing forms, for example as textile threads, yarns, fibre fleeces, padding, flocculated materials or as textile fabrics or textile laminates, knitwear, papers, cardboards and the like.
The new stabilizers may also be used, for example, as follows:
a. In cosmetics, such as perfumes, dyed or undyed soaps and bath salts, skin and face creams, powders, repellants and especially sunburn oils and creams;
b. in admixture with dyestuffs or pigments or as additives to dyebath, printing, discharge or reserve pastes, also for after-treating dyeings, prints or dis charge prints;
c. in admixture with so-called carriers, antioxidants, other light filters, heat stabilizers or chemical bleaches;
d. in admixture with crosslinking agents or dressing agents such as starch or synthetically produced dressings;
e. in combination with detergents (the detergents and stabilizers may, if desired, be added separately to the washing liquors);
in gelatin layers used in photography;
g. in combination with polymeric vehicles (products of polymerization, polycondensation or polyaddition) in which the stabilizers, if desired in addition to other substances, are incorporated in the dissolved of dispersed form, for example in coating, impregnating or binding agents (solutions, disper sions, emulsions) for textiles, fleeces, papers, leathers;
h. as additives to a wide variety of industrial products to reduce the speed of their ageing, for example as additives to glues, adhesives, paints or the like.
If the protective compounds of this invention are to be used for the treatment of textile organic materials of natural or synthetic origin, for example textile fabrics, they may be applied to the substrate to be protected at any desired phase of the final processing of the latter, such as during a dressing or anticrease finishing or dyeing process or during any other finishing operation, by way of a fixing operation similar to a dyeing process.
Furthermore, the new stabilizers to be used according to this invention may be added to or incorporated with the materials prior to or during their shaping. Thus, for example, they may be added to the moulding or injection moulding compositions used in the manu facture of films, foils, tapes or mouldings or they may be dissolved or dispersed or in any other way finely distributed in the spinning mass before it is spun. The protective compounds may also be added to the starting substances, reaction mixtures or intermediates used in the manufacture of fully synthetic or semisynthetic organic materials, that is to say also before or during the chemical reaction, for example in a polycondensation (including precondensates), in a polymerization (including prepolymers) or in a polyaddition.
An important shpere of application of the stabilizers to be used in the invention consists in incorporating these substances in a protective layer used to protect material placed underneath. This application may take the form of applying the ultraviolet absorber to the surface layer (of a film or of a fibre or of a multidimensional shaped object). This can be done for example similar to a dyeing process, or the active substance may be embedded in a polymer (polycondensate or polyadduct) film by one of the known surface coating meth ods with polymeric substances, or the active substance may be dissolved in a suitable solvent and caused to diffuse or swell into the surface layer. According to another important variant the ultraviolet absorber is em bedded in a self-supporting, substantially twodimensional carrier material, for example a foil or the wall of a vessel, in order to keep ultraviolet rays away from the substance located behind it (relevant examples: shop windows, films. transparent packages. bottles).
From the foregoing it is self-evident that in addition to the protection of the substrate or carrier material containing the ultraviolet absorber also other substances contained in the substrate or carrier material are protected, for example dyestuffs, antioxidants, disinfectants, antistatics and other dressing agents, plasticizers and fillers.
Depending on the type of substance to be protected or stabilized. on its sensitivity or the form in which the protection and stabilization is to be imparted, the requisite amount of stabilizer may vary within wide limits, for example from about 0.01 to 10% by weight, referred to the amount of substance to be protected. For most practical purposes, however, a quantity from about 0.05 to 2% will suffice.
Accordingly, as results from the foregoing, the process for protecting organic materials from the effect of ultraviolet radiation and heat consists in homogeneously distributing a compound of one of the formulae l) to (31) in the organic material to be protected, or applying it to the surface of said material or coating the material to be protected with a filter layer containing one of the compounds mentioned.
In particular, this is advantageously done by homogeneously incorporating a compound of the formulae (1 to (31) in substance or in the dissolved or dispersed form in an amount of 0.05 to 2.0% by weight (referred to the weight of the material to be protected) in the organic material to be protected before the latter undergoes its final shaping.
If the substance to be used according to this invention is to be applied to the surface of the substrate to be protected, thus for instance a fibrous material (fabric), this is advantageously done by immersing the substrate to be protected in a liquor in which the oxalic acid diarylamides are dissolved or dispersed. Suitable relevant solvents are, for example, methanol, ethanol, acetone, ethyl acetate, methylethylketone, cyclohexanol and above all water. The substrate to be treated is left in the liquor for some time, similar to the way that dyeing processes are carried out; as a rule, 10 minutes to 24 hours at l0to C suffice, during which, if desired, the liquor may be agitated. Finally, the material is rinsed, if necessary washed, and dried.
In many cases it is of advantage to use the light filters mentioned above in combination with sterically hindered phenols or esters of thiodipropionic acid or organic phosphorus compounds. It is thus in many cases possible to achieve at the same time an anti-oxidation effect; above all, when compounds of the formula l l are used, synergistic effects are observed.
MANUFACTURING EXAMPLES AND INSTRUCTIONS Unless otherwise indicated, parts and percentages in the following manufacturing examples and instructions are by weight.
Furthermore, unless otherwise shown in detail, alkyl groups (C,,H are always n-alkyl groups.
A. A mixture of 44 parts of oxalic acid diethyl ester and 74 parts of para-anisidine in 300 parts of diehlorobenzene is heated and stirred overnight at C under nitrogen. To complete the reaction, the temperature is then raised to C while at the same time distilling off the alcohol. On completion of the reaction, the batch is cooled, the precipitated product suctioned off and washed with benzene and petroleum ether, to yield 78 parts of a product of the formula mi Mace" CO---E\'II 5 The analytically pure product, obtained by recrystallization from dimethylformamide, melts at 270 to 271C.
calculated: C 63.99 found: C 64.10
B. 13,6 Parts of the compound of the formula are suspended in 150 parts of chlorobenzene, and 15.3 parts of acetic anhydride are added.
The reaction mixture is then heated until all has dissolved. To complete the reaction the batch is refluxed for another 2 hours (addition of more acetic anhydride at the boil accelerates and completes the reaction).
The batch is cooled in an ice bath, mixed with 300 parts of methanol, and the precipitated product is suctioned off, to yield 15.05 parts melting at l8l.5 to 185C. After two recrystallizations the product of the formula C l w OCH 011 000 NH- CO-- CO NI is obtained: in theanalytically pure from it melts at 184 to 185C.
calculated: C 60.67 found: C 60.37
For the esterification of the phenolic hydroxyl group by the above method there may be used instead of anhydrides also aliphatic or aromatic acid chlorides.
C. 27.2 Parts of the compound of the formula Oil istoo -00 are taken up in 200 parts of dimethylsulphoxide and mixed with 28 parts of potassium carbonate and 40 parts of octylbromide, then stirred for 6 hours at 50 to 55C. The reaction solution is then mixed with 200 parts of methanol and the precipitated product of the formula is suctioned off and washed with methanol. Yield: 33 parts. The analytically pure product melts at 214 to 215.5C.
C ,H,, O,N.
calculated: C 7254 found: C 72.48
D. A mixture of 146 parts of oxalic acid diethyl ester, 32.2 parts of meta-trifluoromethylaniline and 1 part of boric acid is stirred for 5 hours at to C, with the alcohol formed being continuously distilled off. The melt is then dissolved in dimethylformamide and the product of the formula 5?) N S? E? F -C-C-l'i-" is precipitated with water. Yield, about 33 parts. The analytically pure product obtained by two recrystallizations from alcohol melts at 160 to 161C and reveals the following data:
m iu -2 2 n calculated: C 51.08 found: C 51.28
E. 29.7 Parts of the compound (50) shown in Table A [prepared as described in Example A] are suspended in 400 parts of dimethylformamide and hydrogenated under atmospheric pressure in the presence of Raney nickel until the theoretical quantity of hydrogen has been absorbed (duration: 4 /2 hours; temperature raised up to 125C). The catalyst is filtered off and water is added at the boil until a turbidity appears. After cool- F. When in the method described in Example A the paraanisidine is replaced by the calculated quantity of paraaminobenzoic acid, the product 0 Q g i C) mm. ""NH- 7 HO H (59) is obtained in a yield of 82%. It does not melt below 330C and reveals the following analytical data:
CHEHIZZOGNZEZ calculated: C 58.54 found: C 58.29
H 3.68 N 8.53% H 3.68 N 8.5471
89.3 Parts of the above compound (39) are suspended in 650 parts of thionylchloridc and 5 parts of dimethylformamidc and stirred and refluxed for 7 hours, during which the finely granular suspension turns into crystalline needleswithout dissolving completely. The batch is cooled. rapidly suctioned and rinsed with petroleum ether. The crude product is dried for a short time in a vacuum cabinet and then boiled for minutes with 1400 parts of dichlorobenzene. The undissolved matter is filtered off and the filtrate concentrated to two-thirds its volume. After cooling, the product in the form of needles is suctioned off and washed with petroleum ether, and dried, to yield 71.6 parts of the compound of the formula I which melts at 280C with decomposition and reveals the following analytical data:
m m -l z -z calculated: C 52.63 H 2.76 N 7.67 H 19.42% found: C 53 02 H 2.80 N 7.70 H 18.987!
which, upon recrystallization from dimethylsulphoxide+alcohol. melts at 319 to 321C and reveals the following analysis:
calculated: C 69.78
H 8.4 N 10.17% found: C 69.81 H 8 l 14.6 Parts of the-compounds are suspended in an autoclave in 200 parts of dichlorobenzene. 3.4 parts of liquid ammonia are poured in portionwise and the whole is allowed to react for 2 hours each at C, C and C. The suspension is then steamdistilled and the dried residue extracted for 15 minutes each with 200 parts of dichlorobenzene and then with 200 parts of dimethylformamide. The dried residue (5.5 parts) corresponds to the formula and does not melt below 350C.
lH H i 4 calculated: C 58.89 found: C 58.90
The compounds listed in the following Tables are accessible in an exactly analogous manner:
-- NH 1n the following Table A 35 y Column 1 formula number I Column 11 structural formula NH-CH- (CH Column 111 melting point (uncorrected) in 4C l 2 Column IV analytical data: C H N upper line calculated 5 40 lower line found" t. p. --v
I I I I I I IV ocll H. 00 I w I H 252 254 63-99 5.37 9.53
NI1 cllll 63.99 5-36 9-43 [I l] V 0 0 NCCN 71.92 6.03 10.59 H 11 11 H 275 Cl Cl H ll ll H 295-5 -Continued I II III IV 00 H' 95. (I 25 86 74.95 9.95 4.60 NHCO 74 .71 9.86 4.63 2 87 m1-co---- HH-CO 240.5 77.65 4.74 8.2.5
3 142 73.87 9.48 5.07 OCH -\LJ- OO 97. EFF-O28 moo 41-93 4.02 12.20
Tables B umn I formula number; column II substituent Z in In the following Tables B1 to B12 there are summarizcd compounds corresponding to formula (ll) and l2). and l3) to (24) respectively. In these Tables collower line f0 und.
the preceding formula; column Ill melting point (uncorrected) in C; and column IV analytical data for C, H and N. the upper line being calculated and the
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|U.S. Classification||560/138, 562/457, 560/29, 524/220, 560/134, 562/456, 560/31, 560/139, 252/392, 562/451, 560/45, 564/160, 564/135, 560/140, 560/141, 562/453, 560/47, 562/435, 560/32, 562/455, 564/82, 564/86, 562/442, 560/108, 524/219, 562/52, 562/42, 560/48, 560/133|
|International Classification||C09K15/22, C09K15/00|